CN109851575A - The removal methods of organic acid in epoxyalkane production - Google Patents
The removal methods of organic acid in epoxyalkane production Download PDFInfo
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Abstract
The present invention relates to the removal methods of organic acid in a kind of production of epoxyalkane, comprising: a) provides the first logistics that organic hydroperoxide is obtained with epoxidation reaction of olefines, containing epoxyalkane, benzylalcohol, organic acid and the hydrocarbon corresponding to the organic hydroperoxide；B) first logistics enters the first knockout tower, and tower top obtains the second logistics, and tower bottom obtains third―party logistics；Control 5~30 weight % that third―party logistics alkylene oxide hydrocarbon content is the first logistics alkylene oxide hydrocarbon content；C) third―party logistics enter the second knockout tower, and tower top obtains the 4th logistics of the hydrocarbon containing organic acid and corresponding to the organic hydroperoxide, and tower bottom obtains the 5th logistics.The method can be used in the industrial production of epoxyalkane removing organic acid.
Description
Technical field
The present invention relates to the removal methods of organic acid in a kind of production of epoxyalkane.
Background technique
1,2- epoxy butane is a kind of important organic compound raw material, can be used for preparing polyether polyol, referred to as poly-
Ether.It is limited by 1,2- epoxy butane production technology, common polyethers is mainly currently on the market with ethylene oxide or propylene oxide
Raw material monomer synthesis, with 1,2- epoxy butane be monomer synthesis polyethers due to its own characteristic, purposes is constantly widened.1,2-
Epoxy butane can also be used in production 1,2- butanediol, for manufacturing plasticizer；Butanolamine is produced, coatings industry is used for；1,2- ring
The block copolymer of oxygen butane and ethylene oxide can be used for producing the surfactants such as emulsifier, demulsifier；1,2- epoxy butane
It is also used as the raw material of production fungicide, preservative, also has extensive use in field of medicaments.
Industrially, 1,2- epoxy butane is mainly derived from the byproduct recycling of production of propylene oxide.It is passed through with cracking tail gas
During hypochlorination produces ethylene oxide, propylene oxide, propylene oxide bottom product can be obtained, wherein 1,2- epoxy butane contains
Amount up to 74.6%, there are also a small amount of propylene oxide, ethylene oxide, water and high-boiling components.It, can after distillation, condensing, going water removal
Obtain the 1,2- epoxy butane finished product that content is about 87%.But this method process is longer, and product purity is not high, and yield is relatively fewer.
Chlorohydrination technique is a kind of traditional processing technology for producing 1,2- epoxy butane, makes 1- butylene chlorine with hypochlorous acid first
Refine, then epoxidation.But chlorohydrination production technology needs to consume a large amount of chlorine, the hypochlorous acid pair that production process generates
Equipment seriously corroded, also the generation waste water containing calcium chloride and organic chloride, waste residue, cause greatly to pollute to environment.By
In serious problem of environmental pollution, chlorohydrination has been eliminated substantially.
Document CN104230856A, CN104098532A and CN104177314A, which are disclosed, obtains 1,2- ring using CHP legal system
The production method of oxygen butane, for cumyl hydroperoxide method (CHP method) with cumyl hydroperoxide (CHP) for oxidant, CHP makes 1-
Butylene epoxidation obtains 1,2- epoxy butane and α, alpha-alpha-dimethyl benzylalcohol, α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis generation isopropylbenzene, isopropyl
CHP is generated after benzene oxidatoin to be recycled.The technique can directly mass production 1,2- epoxy butane, process is simple, catalyst stabilization
Property it is good, it is a kind of environmental-friendly atom economy type 1 that 1,2- epoxy butane product purity is high, and no joint product are substantially pollution-free,
2- epoxy butane new green synthesizing process.
Document CN104003960A, CN104098531A and CN104311512A, which are disclosed, produces 1,2- ring using HPPO method
1,2- ring is made using hydrogen peroxide catalyzed epoxidation 1- butylene in the production method of oxygen butane, hydrogen peroxide oxidation process (HPPO method)
Oxygen butane, production process mainly generate 1,2- epoxy butane and water, and process flow is simple, and product yield is high, without other coproduction
Product, it is substantially pollution-free, it is a kind of environmental-friendly new cleanproduction process.
In technical process using 1, the 2- epoxy butane of CHP method (or EBHP method) production, raw material hydrogen peroxide isopropylbenzene
(or hydrogen peroxide ethylbenzene) is obtained generally by isopropylbenzene (or ethylbenzene) oxidation, in the by-product of isopropylbenzene (or ethylbenzene) oxidation
Containing organic acids such as formic acid, acetic acid, propionic acid, meanwhile, the epoxy of 1- butylene and cumyl hydroperoxide (or hydrogen peroxide ethylbenzene)
Change in reaction also along with the side reaction for generating organic acid.Organic acid in product 1,2- epoxy butane can be to product purification equipment
Or product storage facilities causes to corrode.In the prior art, the method for deacidification can be using the method for alkali cleaning and/or washing.But
Due to the particularity of 1,2- epoxy butane, it is soluble easily in water, and hydrolysis easily occurs with water and generates 1,2- butanediol, causes
A large amount of losses of 1,2- epoxy butane.When table 1 is temperature 45 C, 1,2- epoxy butane dissolves in water and the reality of hydrolysising loss amount
Test data.The solubility of 1,2- epoxy butane is 7g or so, and the amount that hydrolysis generates 1,2- butanediol constantly increases at any time.
Table 1
| Hydrolysis time, hour | Epoxy butane/water, wt% | Butanediol/water, wt% |
| 1 | 7.00% | 0.09% |
| 2 | 7.58% | 0.23% |
| 4 | 7.59% | 0.41% |
| 6 | 7.70% | 0.72% |
In existing document, without reference to the relevant report to organic acid removal methods in the production of 1,2- epoxy butane.
Summary of the invention
The present inventor, the study found that by control distillation process, makes organic acid only contain fraction ring by diligent
It is enriched in the mixture of oxygen alkane, then alkali cleaning washing is carried out to the mixture, so that it may solve the problems, such as that at least one is aforementioned, and
It has thus completed the present invention.
Specifically, the present invention relates to the removal methods of organic acid in a kind of production of epoxyalkane, comprising:
A) provide it is that organic hydroperoxide and epoxidation reaction of olefines obtain, containing epoxyalkane, benzylalcohol, organic acid,
And the first logistics of the hydrocarbon corresponding to the organic hydroperoxide；
B) first logistics enters the first knockout tower, and tower top obtains the second logistics, and tower bottom obtains third―party logistics；Control the
Three logistics alkylene oxide hydrocarbon contents are 5~30 weight %, preferably 5~20 weight % of the first logistics alkylene oxide hydrocarbon content, more
It is preferred that 7~15 weight %；
C) third―party logistics enter the second knockout tower, and tower top is obtained containing organic acid and corresponding to organic hydrogen mistake
4th logistics of the hydrocarbon of oxide, tower bottom obtain the 5th logistics；
D) optionally, second stream purification obtains epoxyalkane, and the 5th logistics enters postorder process.
According to an aspect of the present invention, the organic hydroperoxide is cumyl hydroperoxide, corresponds to peroxidating
The hydrocarbon of hydrogen isopropylbenzene is isopropylbenzene.
According to an aspect of the present invention, the organic hydroperoxide is hydrogen peroxide ethylbenzene, corresponds to hydrogen peroxide
The hydrocarbon of isopropylbenzene is ethylbenzene.
According to an aspect of the present invention, in first logistics, the content of epoxyalkane is 5~40 weight %, benzylalcohol
Content be 5~60 weight %, corresponding to the organic hydroperoxide hydrocarbon content be 10~90 weight %, organic acid
Content is 10~1000ppm.
According to an aspect of the present invention, the epoxyalkane be propylene oxide, epoxy butane or its isomer,
Preferably epoxy butane, more preferably 1,2- epoxy butane.
According to an aspect of the present invention, the organic acid includes at least one of formic acid, acetic acid, propionic acid, butyric acid.
According to an aspect of the present invention, it controls in the 4th logistics corresponding to the weight of the hydrocarbon of the organic hydroperoxide
For 0.2~1.5 times of weight of hydrocarbon for corresponding to the organic hydroperoxide in third―party logistics, preferably 0.3~1.4 times, more
It is preferred that 0.4~1.2 times.
According to an aspect of the present invention, the method also includes: the 4th logistics is through alkali cleaning and/or washing.
According to an aspect of the present invention, the method also includes:
4th logistics enters alkali cleaning water wash system, after contacting with lye and water, obtains water phase and oily phase；The water phase
For brine waste.
According to an aspect of the present invention, the method also includes: it is described oil phase at least part be recycled to first point
From tower；And/or at least part of the oily phase enters epoxyalkane refined unit；And/or at least part of the oily phase
Reflux as the second knockout tower.
Beneficial effects of the present invention: the method for the present invention have the residence time it is short, epoxyalkane dissolution it is low with hydrolysising loss rate,
Generate the few advantage of brine waste amount.Directly soda-wash water is gone to wash compared to reacting product stream, the brine waste amount of generation reduces 60
~92%, epoxyalkane yield improves 3~7%.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
Description of symbols:
The first knockout tower of T1
The second knockout tower of T2
X1 alkali cleaning water wash system
1 first logistics-feed stream
2 second logistics-the first separate column overhead stream
3 third―party logistics the-the first knockout tower tower base streams
4 the 4th logistics-the second separate column overhead stream
5 the 5th logistics the-the second knockout tower tower base streams
The oil phase thing stream of the first knockout tower is recycled back to after 6 alkali cleanings washing
7 lye
8 water
9 brine wastes
10 alkali cleanings washing heel row puts logistics
The oil phase thing stream of the second knockout tower is back to after 11 alkali cleanings washing
The present invention is described in detail with reference to the accompanying drawing, it should be noted however that protection scope of the present invention is simultaneously
It is not limited, it but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all are incorporated by reference into
Herein.Unless otherwise defined, all technical and scientific terms used herein all there are those skilled in the art routinely to manage
The meaning of solution.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made
Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal
It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with
It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards
For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the case where not clearly indicating, all pressure being previously mentioned in this specification are all absolute pressures.
Raw material handled by the method for the present invention is the reaction solution that organic hydroperoxide and epoxidation reaction of olefines obtain.
Organic hydroperoxide and epoxidation reaction of olefines be for disclosed in the prior art, according to the difference of organic hydroperoxide,
Can there are cumyl hydroperoxide method (CHP method) and hydrogen peroxide ethylbenzene method (EBHP method).Epoxyalkane is propylene oxide, epoxy
Butane or its isomer, preferably epoxy butane, more preferably 1,2- epoxy butane.It is to produce 1,2- epoxy butane
Example, for cumyl hydroperoxide method (CHP method) with cumyl hydroperoxide (CHP) for oxidant, CHP obtains 1- butylene epoxidation
1,2- epoxy butane and α, alpha-alpha-dimethyl benzylalcohol, α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis generate isopropylbenzene, generate CHP after cumene oxidation
It is recycled.For producing propylene oxide, hydrogen peroxide ethylbenzene method (EBHP method) is oxidation with hydrogen peroxide ethylbenzene (EBHP)
Agent, EBHP make epoxidation of propylene obtain propylene oxide and α-methylbenzylalcohol, and α-methylbenzylalcohol hydrogenolysis generates ethylbenzene, after ethylbenzene oxidation
EBHP is generated to be recycled.It is (organic containing epoxidation product epoxyalkane and benzylalcohol in the reaction solution that epoxidation reaction obtains
Hydroperoxides are cumyl hydroperoxide, and corresponding benzylalcohol is α, alpha-alpha-dimethyl benzylalcohol；Organic hydroperoxide is peroxidating
Hydrogen ethylbenzene, corresponding benzylalcohol are α-methylbenzylalcohol), with raw material organic hydroperoxide be carried along into corresponding to organic hydrogen
(organic hydroperoxide is cumyl hydroperoxide to the hydrocarbon of peroxide, and the hydrocarbon corresponding to cumyl hydroperoxide is isopropylbenzene；
Organic hydroperoxide is hydrogen peroxide ethylbenzene, and the hydrocarbon corresponding to hydrogen peroxide ethylbenzene is ethylbenzene), the content of epoxyalkane is 5
~40 weight %, the content of benzylalcohol are 5~60 weight %, and the content corresponding to the hydrocarbon of the organic hydroperoxide is 10~90
Weight %.In addition, this has since organic hydroperoxide is aoxidized by the hydrocarbon corresponding to the organic hydroperoxide
Contain the organic acids such as formic acid, acetic acid, propionic acid in the by-product of the hydrocarbon oxidation of machine hydroperoxides；Meanwhile organic hydroperoxide
With, also along with the side reaction for generating organic acid, therefore the reaction that epoxidation reaction obtains is molten in the epoxidization reaction process of alkene
In liquid, also containing the organic acid of 10~1000ppm.In addition, being also possible in the reaction solution that epoxidation reaction obtains containing a small amount of
Aldehyde, ketone, water, C6-C8 hydro carbons and other heavy constituents.
According to the present invention, in Fig. 1, reaction solution (the first object that organic hydroperoxide and epoxidation reaction of olefines obtain
1) stream enters the first knockout tower T1, tower top obtains the second logistics 2 containing the light components such as aldehyde, ketone and PART EPOXY alkane, tower
Bottom is obtained containing C6~C8 hydro carbons, the hydrocarbon corresponding to the organic hydroperoxide, benzylalcohol, water, organic acid, PART EPOXY alkane
Hydrocarbon and the third―party logistics of other heavy constituents 3.Because the relative volatility very little of epoxyalkane and organic acid, is difficult to pass through essence
The method evaporated is kept completely separate, and organic acid enters the second logistics 2 of the first knockout tower T1 overhead extraction in order to prevent, using by small portion
The method for dividing epoxyalkane to produce from tower reactor, control third―party logistics alkylene oxide hydrocarbon content are the first logistics alkylene oxide hydrocarbon content
5~30 weight %, preferably 5~20 weight %, more preferable 7~15 weight %, to guarantee the whole into the first knockout tower T1
Organic acid is all produced from tower reactor.
The operating condition of first knockout tower T1 includes: that tower reactor operation temperature is 100~170 DEG C, and tower top operating pressure is with exhausted
Pressure is calculated as 100~200kPa, and reflux ratio is 1~20.Because benzylalcohol, epoxyalkane are heat-sensitive substance, tower reactor operation temperature
Control is 100~170 DEG C.First knockout tower theoretical cam curve can be 20~50 pieces, feed entrance point be tower top below the 4th~
30 blocks of column plates.
According to the present invention, third―party logistics 3 enter the second knockout tower T2, and tower top is obtained containing epoxyalkane, organic acid, C6~C8
4th logistics 4 of hydro carbons and the hydrocarbon corresponding to the organic hydroperoxide, tower bottom obtain having containing benzylalcohol, corresponding to described
The hydrocarbon of machine hydroperoxides and the 5th logistics 5 of other heavy constituents.In 4th logistics, the content of epoxyalkane is 5~50 weights
% is measured, the content corresponding to the hydrocarbon of the organic hydroperoxide is 50~95 weight %.What is carried in the first logistics as a result, has
Machine acid is all enriched in the 4th logistics, and the amount of the 4th logistics alkylene oxide hydrocarbon is only the amount of the first logistics alkylene oxide hydrocarbon
5~30 weight %, thus greatly reduce because alkali cleaning washing caused by epoxyalkane solution loss and hydrolysising loss.
The operating condition of second knockout tower T2 includes: that tower reactor operation temperature is 100~170 DEG C, and tower top operating pressure is with exhausted
Pressure is calculated as 5~200kPa, and reflux ratio is 1~20.Equally, because benzylalcohol, epoxyalkane are heat-sensitive substance, tower reactor operation temperature
Degree control is 100~170 DEG C.Second knockout tower theoretical cam curve can be 10~40 pieces, and feed entrance point is the 3 below tower top
~25 blocks of column plates.
A preferred embodiment according to the present invention, the method for the present invention further include: the 4th logistics 4 is through alkali cleaning and/or water
It washes.
A preferred embodiment according to the present invention, the method for the present invention further include: the 4th logistics 4 enters alkali cleaning washing system
Unite X1, after contacting with lye 7 and water 8, obtains water phase and oily phase.Water phase is brine waste, into treatment unit for waste water.Oily phase
At least part logistics 6 is recycled to the first knockout tower T1.And/or at least part logistics 11 of oily phase is used as the second knockout tower
Reflux.
According to the present invention, the hydrocarbon corresponding to the organic hydroperoxide in the 4th logistics, in alkali cleaning water-washing process
Serve as the effect of extractant.
A preferred embodiment according to the present invention, to prevent C6~C8 hydro carbons from accumulating in system, especially boiling point
The component between hydrocarbon (isopropylbenzene or ethylbenzene) between epoxyalkane and corresponding to the organic hydroperoxide, such as C8 alkene
Hydrocarbon, mutually a part is used as effluent streams, regular or quantitative discharge to the isolated oil of alkali cleaning water wash system；Control effluent streams 10
Amount account for alkali cleaning washing system oil extraction total amount 0.1~2 weight %.
According to the present invention, the second logistics, the epoxyalkane in effluent streams 10 and correspond to the organic hydroperoxide
The hydrocarbon (isopropylbenzene or ethylbenzene) of object, is recycled into epoxyalkane refined unit.
According to the present invention, the 5th logistics 5 enters postorder process, wherein the benzylalcohol hydrogenolysis contained, hydroformylation product solution are reoxidised into
The organic hydroperoxide of epoxidation reaction of olefines is recycled.
According to the present invention, because epoxyalkane is soluble easily in water, and hydrolysis easily occurs with water and generates glycol, in order to subtract
Few solution loss and hydrolysising loss of the epoxyalkane in alkaline cleaning procedure, by a part corresponding to the organic hydroperoxide
Hydrocarbon (isopropylbenzene or ethylbenzene) is from the second knockout tower T2 overhead extraction together with epoxyalkane, and the part isopropylbenzene or ethylbenzene are in alkali cleaning
The effect of extractant is served as in water wash system.Controlling the weight of hydrocarbon in the 4th logistics corresponding to the organic hydroperoxide is
Corresponding to 0.2~1.5 times, preferably 0.3~1.4 weight % of the weight of the hydrocarbon of the organic hydroperoxide in third―party logistics,
More preferable 0.4~1.2 weight %.
According to the present invention, lye used in alkali cleaning be known in the art, such as can be mass concentration 1~25%
Sodium hydroxide solution or 1~25% sodium carbonate liquor.
Below by specific embodiment, the invention will be further elaborated.
Specific embodiment
[embodiment 1]
As shown in Figure 1, by taking 4000 tons/year BO (epoxy butane) device as an example, wherein in feeding flow stock 1, with weight hundred
Divide than meter, α, the content of alpha-alpha-dimethyl benzylalcohol is 42.2%, and the content of isopropylbenzene is 35.3%, and the content of epoxy butane is
21.3%, the content of organic acid is 630ppm, and the content of octene is 168ppm.
First separation column overhead operating pressure is 130kPaA, and tower top operation temperature is 72 DEG C, and tower reactor operation temperature is 167
℃。
Second separation column overhead operating pressure is 50kPaA, and tower top operation temperature is 121 DEG C, and tower reactor operation temperature is 142
℃。
First knockout tower tower reactor extraction third―party logistics in 1,2- epoxy butane amount Zhan Jinta the first logistics in 1,
The 10.0% of 2- epoxy butane total amount.In 4th logistics of the second knockout tower overhead extraction each component by weight percentage, ring
The content of oxygen butane is 10.4%, and the content of isopropylbenzene is 83.2%, and the content of organic acid is 0.15%, and the content of octene is
4.7%.The weight of isopropylbenzene is 0.48 times of the weight of isopropylbenzene in third―party logistics in 4th logistics.Into the alkali of caustic washing system
Liquid is the sodium hydrate aqueous solution of weight concentration 2.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.64%, and the brine waste amount of generation is 144kg/hr.
[embodiment 2]
With [embodiment 1], change feed composition, in feeding flow stock 1, by weight percentage, α, alpha-alpha-dimethyl benzylalcohol
Content is 35.0%, and the content of isopropylbenzene is 46.1%, and the content of epoxy butane is 17.7%, and the content of organic acid is
530ppm, the content of octene are 168ppm.
First knockout tower operating pressure is 130kPaA, and tower top operation temperature is 71 DEG C, and tower reactor operation temperature is 168 DEG C.
Second knockout tower operating pressure is 50kPaA, and tower top operation temperature is 123 DEG C, and tower reactor operation temperature is 139 DEG C.
1,2- in the first logistics of the amount Zhan Jinta of 1,2- epoxy butane in the third―party logistics of first knockout tower tower reactor extraction
The 10.0% of epoxy butane total amount.In 4th logistics of the second knockout tower overhead extraction each component by weight percentage, epoxy
The content of butane is 9.2%, and the content of isopropylbenzene is 88.6%, and the content of organic acid is 0.16%, and the content of octene is
1.0%.The weight of isopropylbenzene is 0.96 times of the weight of isopropylbenzene in third―party logistics in 4th logistics.Into the alkali of caustic washing system
Liquid is the sodium hydrate aqueous solution that weight concentration is 2.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.62%, and the brine waste amount of generation is 145kg/hr.
[embodiment 3]
With [embodiment 1], change feed composition, in feeding flow stock 1, by weight percentage, α, alpha-alpha-dimethyl benzylalcohol
Content is 55.0%, and the content of isopropylbenzene is 15.8%, and the content of epoxy butane is 28.0%, and the content of organic acid is
630ppm, the content of octene are 168ppm.
First knockout tower operating pressure is 130kPaA, and tower top operation temperature is 72 DEG C, and tower reactor operation temperature is 166 DEG C.
Second knockout tower operating pressure is 50kPaA, and tower top operation temperature is 119 DEG C, and tower reactor operation temperature is 154 DEG C.
1,2- in the first logistics of the amount Zhan Jinta of 1,2- epoxy butane in the third―party logistics of first knockout tower tower reactor extraction
The 10.0% of epoxy butane total amount.In 4th logistics of the second knockout tower overhead extraction each component by weight percentage, epoxy
The content of butane is 12.3%, and the content of isopropylbenzene is 74.8%, and the content of organic acid is 0.14%, and the content of octene is
11.7%.The weight of isopropylbenzene is 1.08 times of the weight of isopropylbenzene in third―party logistics in 4th logistics.Into caustic washing system
Lye is the sodium hydrate aqueous solution that weight concentration is 2.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.55%, and the brine waste amount of generation is 108kg/hr.
[embodiment 4]
With [embodiment 1], the lye into caustic washing system is changed to the sodium hydrate aqueous solution that weight concentration is 2.4%.
As a result are as follows: the yield of 1,2- epoxy butane is 98.97%, and the brine waste amount of generation is 121kg/hr.
[embodiment 5]
With [embodiment 1], the lye into caustic washing system is changed to the sodium hydrate aqueous solution that weight concentration is 5.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.86%, and the brine waste amount of generation is 58kg/hr.
[embodiment 6]
With [embodiment 1], the lye into caustic washing system is changed to the sodium hydrate aqueous solution that weight concentration is 10.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.89%, and the brine waste amount of generation is 29kg/hr.
[embodiment 7]
With [embodiment 1], the lye into caustic washing system is changed to the aqueous sodium carbonate that weight concentration is 10.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.88%, and the brine waste amount of generation is 77kg/hr.
[embodiment 8]
With [embodiment 1], the lye into caustic washing system is changed to the aqueous sodium carbonate that weight concentration is 5.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.83%, and the brine waste amount of generation is 153kg/hr.
[embodiment 9]
With [embodiment 1], the lye into caustic washing system is changed to the aqueous sodium carbonate that weight concentration is 15.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 99.92%, and the brine waste amount of generation is 51kg/hr.
[embodiment 10]
With [embodiment 1], change the ratio of 1, the 2- epoxy butane of the first knockout tower tower reactor extraction, the first knockout tower tower reactor
The 5.0% of the 1,2- epoxy butane total amount of the amount Zhan Jinta of the 1,2- epoxy butane of extraction.
First knockout tower operating pressure is 130kPaA, and tower top operation temperature is 71 DEG C, and tower reactor operation temperature is 172 DEG C.
Second knockout tower operating pressure is 50kPaA, and tower top operation temperature is 124 DEG C, and tower reactor operation temperature is 142 DEG C.
By weight percentage, the content of epoxy butane is 5.3% to each component in the logistics of second knockout tower overhead extraction,
The content of isopropylbenzene is 89.3%, and the content of organic acid is 0.15%, and the content of octene is 4.0%.Isopropylbenzene in 4th logistics
Weight be 0.51 times of weight of isopropylbenzene in third―party logistics.It is 2.0% that lye into caustic washing system, which is weight concentration,
Sodium hydrate aqueous solution.
As a result are as follows: the yield of 1,2- epoxy butane is 99.78%, and the brine waste amount of generation is 144kg/hr.
[embodiment 11]
With [embodiment 1], change the ratio of 1, the 2- epoxy butane of the first knockout tower tower reactor extraction, the first knockout tower tower reactor
The 20.0% of the 1,2- epoxy butane total amount of the amount Zhan Jinta of the 1,2- epoxy butane of extraction.
First knockout tower operating pressure is 130kPaA, and tower top operation temperature is 71 DEG C, and tower reactor operation temperature is 158 DEG C.
Second knockout tower operating pressure is 50kPaA, and tower top operation temperature is 116 DEG C, and tower reactor operation temperature is 142 DEG C.
By weight percentage, the content of epoxy butane is each component in the logistics of second knockout tower overhead extraction
20.1%, the content of isopropylbenzene is 71.7%, and the content of organic acid is 0.13%, and the content of octene is 7.4%.In 4th logistics
The weight of isopropylbenzene is 0.43 times of the weight of isopropylbenzene in third―party logistics.Lye into caustic washing system is for weight concentration
2.0% sodium hydrate aqueous solution.
As a result are as follows: the yield of 1,2- epoxy butane is 99.28%, and the brine waste amount of generation is 144kg/hr.
[comparative example 1]
Unlike [embodiment 1], using single-tower operation, feeding flow stock 1 is directly entered alkali cleaning water wash system, to all
Material carries out alkali cleaning washing, and the lye into caustic washing system is the aqueous sodium carbonate that weight concentration is 2.0%.
As a result are as follows: the yield of 1,2- epoxy butane is 97.10%, and the brine waste amount of generation is 383kg/hr.
[comparative example 2]
Unlike [embodiment 1], using single-tower operation, the material of the first knockout tower overhead extraction enters alkali cleaning washing
System carries out alkali cleaning washing to all tower top materials, and the lye into caustic washing system is the sodium carbonate that weight concentration is 2.0%
Solution.
As a result are as follows: the yield of 1,2- epoxy butane is 93.00%, and the brine waste amount of generation is 383kg/hr.
Claims (10)
1. the removal methods of organic acid in a kind of epoxyalkane production, comprising:
A) provide it is that organic hydroperoxide and epoxidation reaction of olefines obtain, containing epoxyalkane, benzylalcohol, organic acid and
Corresponding to the first logistics of the hydrocarbon of the organic hydroperoxide；
B) first logistics enters the first knockout tower, and tower top obtains the second logistics, and tower bottom obtains third―party logistics；Control third object
Flow 5~30 weight % that alkylene oxide hydrocarbon content is the first logistics alkylene oxide hydrocarbon content, preferably 5~20 weight %, more preferable 7
~15 weight %；
C) third―party logistics enter the second knockout tower, and tower top is obtained containing organic acid and corresponding to the organic hydroperoxide
4th logistics of the hydrocarbon of object, tower bottom obtain the 5th logistics；
D) optionally, second stream purification obtains epoxyalkane, and the 5th logistics enters postorder process.
2. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that organic hydrogen mistake
Oxide is cumyl hydroperoxide, and the hydrocarbon corresponding to cumyl hydroperoxide is isopropylbenzene.
3. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that organic hydrogen mistake
Oxide is hydrogen peroxide ethylbenzene, and the hydrocarbon corresponding to cumyl hydroperoxide is ethylbenzene.
4. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that first logistics
In, the content of epoxyalkane is 5~40 weight %, and the content of benzylalcohol is 5~60 weight %, corresponds to the organic hydroperoxide
The content of the hydrocarbon of object is 10~90 weight %, and the content of organic acid is 10~1000ppm.
5. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that the epoxyalkane
For propylene oxide, epoxy butane or its isomer, preferably epoxy butane, more preferably 1,2- epoxy butane.
6. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that the organic acid packet
Include at least one of formic acid, acetic acid, propionic acid, butyric acid.
7. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that control the 4th logistics
In corresponding to the organic hydroperoxide hydrocarbon weight be third―party logistics in correspond to the organic hydroperoxide hydrocarbon
0.2~1.5 times, preferably 0.3~1.4 times, more preferable 0.4~1.2 times of weight.
8. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that the method is also wrapped
It includes:
4th logistics is through alkali cleaning and/or washing.
9. according to claim 1 epoxyalkane production in organic acid removal methods, which is characterized in that the method is also wrapped
It includes:
4th logistics enters alkali cleaning water wash system, after contacting with lye and water, obtains water phase and oily phase；The water phase be containing
Salt waste water.
10. according to claim 9 epoxyalkane production in organic acid removal methods, which is characterized in that the method is also
Include:
At least part of the oil phase is recycled to the first knockout tower；And/or
At least part of the oil phase enters epoxyalkane refined unit；And/or
Reflux of at least part of the oil phase as the second knockout tower.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723637A (en) * | 1995-12-06 | 1998-03-03 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
| JP2003183265A (en) * | 2001-12-19 | 2003-07-03 | Sumitomo Chem Co Ltd | Propylene oxide rectifier |
| CN104926759A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for preparation of epoxypropane |
| CN105367520A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Method for preparing propylene oxide |
-
2017
- 2017-11-30 CN CN201711237478.6A patent/CN109851575B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723637A (en) * | 1995-12-06 | 1998-03-03 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
| JP2003183265A (en) * | 2001-12-19 | 2003-07-03 | Sumitomo Chem Co Ltd | Propylene oxide rectifier |
| CN104926759A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for preparation of epoxypropane |
| CN105367520A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Method for preparing propylene oxide |
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